Certain oxyalkylated glucoses



y 1960 M. DE GROOTE EI'AL 2,945,025

CERTAIN OXYALKYLATED GLUCOSES Original Filed May 24-, 1954 C4Ha0 StatesCERTAIN F'OXYALKYLATED GLUCOSES Melvin ne' Groote, St. 'Louis, and OwenH. Pettingill,

Kirkwood, Mo., assignors to- Petrolite Corporation, Wilmington, Del.,acorporation of Delaware 'Q'riginal application May 24, 1954,Ser. No.'431,7 90.

' Divided and this application May 27, 1957, Ser.*No. 661,738

1 '10 Claims. 01. zen- 209 This applicationis" a division of ourcopending application Serial No. 431,790, filed May 24, 1954.

Our invention is concerned with new chemical products or compoundsuseful as demulsifying agents in processes "or procedures particularlyadapted for preventing, breaking or resolving emulsions of thewater-in-oil type and particularly petroleum emulsions. I concerned withthe application of such chemical products Our invention is also orcompounds in various other arts and industries as well as with'methodsof manufacturing the new chemical products or compounds which are ofoutstanding value in demulsification.

More specifically then the present invention is concerned withaco'generic mixture of homologous'series of glycol ethers of glucose.The cogeneric mixtures are derived exclusively from glucose, ethyleneoxide, propylene oxide and butylene oxide, in such weight proportions 6.However, as will 'be pointed out subsequently the same ultimatecompositions may be employed using any one of the three oxides last.

The oxyalkylation of glucose by means of ethyene oxide, propylene oxide,or butylene oxide has been described in the literature. One can useinstead of the oxides the corresponding alkylene carbonates, towit,ethylene carbonate, propylene carbonate, or butylene carbonate.

As is well known, the oxyalkylation derivatives from anyoxyalkylation-su'sceptible compound, are prepared by the additionreaction between such oxides and such compound. The addition reaction isadvantageously carried out at an elevated temperature and pressure andin the presence of a small amount of alkaline catalyst. Usually, thecatalyst is sodium hydroxide or sodium met-hylate. The reactiontemperature is apt to be 140 C. or somewhat less, and the reactionpressure not in excess of 30 to 50 pounds per square inch. The reactionproceeds rapidly. See, for example, U.S. Patent No. 2,636,- 038, datedApril 21, 1953, to Brandner.

'As to further information in regard to the mechanical steps involved inoxyalkylation, see U.S. Patent No. 2,499,365, dated March 7, '1950, toDe Grooteet a1. Particular reference is made to columns 92 et seq.

The oxyalkylation of a liquid or a solid which can be melted atcomparatively low temperature (under 150 C.) without decompostion or issoluble in an inert solvent, such as xylene, presents little or nomechanical difliculties in the oxyalkylation step. When one has a "Slldwhichcannot be melted, or decomposes on meltas 'in the case'of theoxyalkylation of sucrose.

2,9i5,5 Patented July 12, 1930 See U.S.

Patent No. ;2,652,394, dated September-15, 19 53, to De Groote.xylene-insoluble solid in xylene the procedure is sub- Actually, as faras oxyalkylating a slurry of a 'f' stantially the same forpentaerythritol, or sorbitol,or

sucrose, or for that matter, for glucose.

butylene oxide or the equivalents.

The oxyalkylation of glucose can be accomplished in a number of ways andthe particular procedure is immaterial. Such procedure has beendescribed in numero'us patentsand specific reference is made to theinstant application which is concerned with ethylene oxide and Actually,whether one uses ethylene oxide or butylene oxide or, for that matter,propylene oxide one preferably starts with powdered glucose suspended ina slurry in xylene or a similar' unreactive solvent; or one employs analkylene carharry 27, 1953, to De Groote.

bonate such as ethylene carbonate, butylene carbonate or propylenecarbonate for theinitial oxyalkylation. When such initial oxyalkylationhas gone far enough to convert tol in the form of a slurry. Such slurryis the equivalent of a'slurry 'of'powdered glucose.

In the use of butylene oxide the same procedure can 5 be employed as isdescribed in the use of propylene oxide 'and'the oxypropylation of'glucose as described in U.S. Patent No. 2,626,935, dated Janauary 27,1953.

' For instance, we have found we can oxybutylate glucose in the samemanner that is used conventionally'for oxypropylation. For example, Wehave followed the directions which appear in columns 7, 8 and 9 ofaforementioned U.S. Patent 2,626,935 in regard to the oxyethylation' oroxypropylation of glucose and find itis just as I suitable in connectionwith butylene oxide. We have completed the reactions under the sameconditions set forth inExamples 1a through 4a using propylene oxide andvaried the procedure only in that the time required was somewhatslightly longer.

" Other" patents include specific information as to the oxypropylationof sugars or similar products including glucose. Actually the procedureis substantially the same Whether one uses propylene, ethylene, orbutylene oxide. It is not believed any examples are necessary toillustrate such well known procedure but for purpose of illustration thefollowing are included:

Example 101 The reaction vessel employed was a stainless steel autoclavewith the usual devices for. heating, heat control, stirrer, inlet,outlet, etc., which is conventional in this type of apparatus. Thecapacity was approximately 4 liters. The stirrer operated at a speed ofapproximately 250 rpm. There were charged into the autoclave 500 gramsof glucose, 300 grams of xylene, and 15 grams of sodium methylate. Theautoclave was sealed, swept with nitrogen gas and stirring startedimmediately and heat applied. The temperature was allowed to rise to'approximately C. At this particular time the addition of butylene oxidewas started. The butylene oxide employed was a mixture of the straightchain isomer substantially freefrom isobutylene oxide. It was addedcontinuously, at such speed that it was ab- "sorbed bythe reaction asadded. The amount addedin Example 2a The reaction mass was transferredto a larger autoclave (capacity 15 liters). Without adding any moresolvent or any more xylene the procedure was repeated 'so as to addanother 1500 grams of butylene oxide under substantially the sameoperating conditions but requiring about 3 hours for the addition. Atthe end of this step the ratio represented approximately 6 to 1 (ratiobutyleneoxide to glucose).

Example 3a In a third step, instead of adding 1500 grams of butyleneoxide, 1625 grams were added. The reaction slowed up and requiredapproximately 6 hours, using the same operating temperatures andpressures. The ratio at the end of the third step was 9.25 parts byweight of butylene oxide per'weight of glucose.

Example 4a 7 At' the end of this step, the autoclave was opened and anadditional grams of sodium methylate added, the

autoclave flushed out as before, and the fourth and final oxyalkylationcompleted, using 1625 grams of butylene oxide, and the oxyalkylation wascomplete within 3% hours using the same temperature range and pressureas previously. At the end of the reaction the product representedapproximately 12.5 parts of butylene oxide by weight to one part ofglucose.

All the examples, except the first step, were substantiallyWater-insoluble and xylene-soluble.

' As has been pointed out previously these oxybutylated glucoses weresubjected to oxyethylation in the same manner described in respect tothe oxypropylated glucose in aforementioned U.S. Patent No. 2,626,935.Indeed, the procedure is comparatively simple for the reason that one isworking with a liquid and also that ethylene oxide is more reactive thanbutylene oxide. As a result, using the same amount of catalyst one canoxyethylate more rapidly than usually at a lower pressure. There is nosubstantial difference as far as operating procedure goes whether one isoxyethylating oxypropylated glucose or oxybutylated glucose.

The same procedure using a slurry of finely powdered glucose in xylenewas employed in connection with ethylene oxide and the same mixture on apercentage basis was obtained as in the above examples where butyleneoxide and glucose were used.

The same procedures have been employed using other butylene oxidesincluding mixtures having considerable isobutylene oxide and mixtures ofthe straight chain isomers with greater or lesser amounts of the 2,3isomer.

Where reference has been made in previous examples to straight chainisomer, the product used was one which was roughly 85% or more of the1,2 isomer and approximately of the 2,3-cisand the 2,3-trans-isomer withsubstantially none or not over 1% of the isobutylene oxide.

In the preceding procedures one oxide has been added and then the other.One need not follow this procedure. The two oxides can be mixed togetherin suitable proportions and subsequently subjected to jointoxyalkylation so as to obtain products coming within the specifiedlimits. In such instances, of course, the oxyalkylation may be describedas random oxyalkylation insofar that one cannot determine the exactlocation of the butylene oxide or ethylene oxide groups. In suchinstances the procedure again is identically the same as previouslydescribed and, as a matter of fact, we have used such methods inconnection with molten sorbitol.

If desired, one may add part of one oxide and all of the other and thenreturn to the use of the first oxide, for instance; or one may use theprocedure as previously, adding first some butylene oxide, then ethyleneoxide and then the butylene oxide. Or, inversely, one may add someethyleneoxide, then all butylene oxide and then the remainder of theethylene oxide; or either oxide could be added, in portions so thatfirst one oxide is added, then the other, then the first oxide is addedagain, and then very convenient way of oxyethylating glucose.

it can be oxyethylated without the use of pressure. Such procedure, andparticularly melting the carbonate first the second oxide. We have foundno advantage in so doing. Indeed, our preferencehas been to add all thebutylene oxide first and then the required amount of ethylene oxide.

As pointed out previously,'glucose can be oxyethylated in the same wayit is oxybutyl-ated, i.e., by preparing a slurry in xylene or in asimilar solvent and using a suitable alkaline catalyst such as causticsoda, sodium methylate, or the like, and then adding the ethylene oxide.The changes previously mentioned are of difference in degree only. Inother words, oxyethyl-ation will take place at a lower temperature, forinstance, top temperature of probably 130 to 135 C. instead of 145 to150 C. The same weight of ethylene oxide could be added in 75% to 85% ofthe time required for butylene oxide. The pressure during the reaction,instead of being to pounds as in the case of butyleneoxide, is apt to be10 to 15 pounds and at times a little higher. Otherwise, there is nodifference.

Also, if .desired, the use of ethylene carbonate is a In fact,

and adding the powdered glucose slowly permits the production of areaction mass which is a liquid or which melts readily at comparativelylow temperatures to yield a liquid. Such reaction should be conducted insuch a way that there is no residual ethylene carbonate or for thatmatter propylene carbonate when the mass is trans- .ferred to anautoclave. In fact, propylene carbonate is more satisfactory thanethylene carbonate.

One can oxyalkylate using an acid catalyst or an alkaline catalyst or atleast in part, without the use of any catalyst although such procedureis extremely slow and uneconomical. In other words, any one of theconventional catalysts used in oxyalkylation may be employed. It is ourpreference, however, to use an alkaline catalyst such as sodiummethylate, caustic soda, or the like.

Actually, finely powdered glucose may contain a trace of moisture. Ourpreference is to prepare the slurry with an excess of xylene and distilloff one part of the xylene was to remove any trace of water and thenflush out the mass with nitrogen. Even so, there may be a few tenths ofa percent of moisture remain although at times examination indicates atthe most it is mere-1y a trace.

Actually; the oxyalkylation of glucose, particularly if one uses aslurry in aninert solvent such as xylene,

proceeds satisfactorily in the same manner described in U.S. Patent No.2,552,528, dated May 15, 1951, to De Groote, wherein the productsubjected to oxyalkylation is sorbitol. .When butylene. oxide is usedthe same procedure can be followed as in the use of propylene oxide asdescribed in Example A in .Part 2 of the aforementioned U.S. .Patent2,552,528.; or, if desired, butylene oxide can be used andthesameprocedure can be followed as in the use ofpropylene oxide asdescribed in Example la of the aforementioned U.S. Patent 2,626,935. Thefinely powdered glucose is stirredtwith a solvent, such as diethyletherof diethyleneglycol or, for that matter one may use ethylene glycoldimethylether, diethylene glycol dimethyl ether, triethylene glycoldimethyl ether, or tetra ethyleneglycol dimethyl ether. Asoxybuty-lation proceeds the reaction mass becomes a homogeneous mass.

Referring momentarily to U.S. Patent No. 2,552,528, the finely powderedsorbitol is reacted with butylene oxide and as oxybutylation takes placethereaction mass becomes a homogeneous liquid. For instance, referringto Example A, column ,16 of aforementioned patent,

we have used identically the sameprocedure starting with anhydrousfinely powdered glucose. .Instead of using 1600 grams of propyleneoxide, there. was used 1800 grams of butylene oxide (mixed straightchain isomers).

In Example B, instead of using 1100 grams of the propylene oxide derivedintermediate from Example A, preceding, there was used instead-1191grams of the butylene oxide derived intermediate, Example A. Instead ofusing 1327 grams of propylene oxide, there was added 1493 grams ofbutylene oxide. I a v In Example C, instead of using 1149 grams ofpropylene oxide derived intermediate Example B, from the precedingexample, there was used instead 1271' grams of butylene oxide derivedintermediate B. Insteadof adding 1995 grams of propylene oxide in thisstage, there was added instead 2345 grams of, butylene oxide.

In Example D, instead of 743 grams of the propylene oxide derivedintermediate from Example C, preceding, there was used 831 grams of thebutylene oxide derived intermediate. Instead of adding 637 grams ofpropylene oxide in this stage, there was added 717 grams of butyleneoxide.

It will be noted at this stage the ratio of butylene oxide to glucosewas approximately 100-to-1, and the amount of glucose represents lessthan 3%, by Weight, of the end product and the amount of butylene oxiderepresented over 97%.

Example E was conducted in the same manner except that the initialreactant was Example D, preceding, and instead of using 566 grams, therewas used instead 628 grams of the reactant. Instead of adding 563 gramsof propylene oxide, there was added instead 633 grams of butylene oxide.

In this last example, five grams of sodium methylate were added as acatalyst to speed up the final stage of reaction. Operating conditions,such as temperature, time factor, etc., were substantially the same asdescribed in the corresponding Examples A, B, D, C, and E, inaforementioned US, Patent 2,552,528. a

It will be noted that in this final product approximately 200 moles ofbutylene oxide Were employed per mole of glucose. On a percentage basis,the products represented approximately 1% glucose and 99% butyleneoxide.

All examples, except the first stage, were substantially water-insolubleand xylene soluble.

It is immaterial in what order the oxides are added to glucose, so as toobtain the herein described products.

However, our preference is to add butylene oxide first,-

on2on-orn on,

CHs-CHCH-CHa or a mixture of the two.

As noted previously, one can oxyethylate' first and then add either oneof the other two oxides, to wit, butylene oxide or propyleneoxide.Similarly, one can add either oxide first, that is, propylene oxide orbutylene oxide, and then add'ethylene oxide, followed by the addition ofthe other oxide. Also, as is obvious, one need not add all the ethyleneoxide alone or all the butylene oxide alone or all the propylene oxidealone. One could make a mixtureof either one of the two, or all three,and use such mixture or mixtures as an oxyalkylating agent. Furthermore,one can add a fraction of any particular oxide and then add the rest ata subsequent stage This may be applied not only to. a single oxide butalso to two of the three, or all three, of the oxides employed.

The products of the present invention are also useful for variouspurposes other than the resolution of petroleumemulsions'of thewater-in-oil type.

The new products are useful as wetting, detergent and leveling'agents inthe laundry, textile and dyeing industries; as wetting agents anddetergents in the acid-washing of building stone and brick; as wettingagents and spreaders in the application of asphalt in road building andthe like; as aflotation reagent in the flotation separation of variousaqueous suspensions containing negatively charged particles, such assewage, coal washing, Waste water, and various trade wastes and thelike; as germicides, insecticides, emulsifying agents, as, for example,for cosmetics, spray oils, water-repellent textile finishes; aslubricants, etc.

For the purposeof resolving petroleum emulsions of the water-in-oiltype, and also for that matter for numerous other purposes wheresurface-active materials are effective, and particularly for those usesspecified elsewhere herein, we prefer to employ oxyalkylatedderivatives, which are obtained by the use of monoepoxides,

in such manner that derivatives so obtainedhave sufficient hydrophilecharacter to meet at least the test set forth in U.S. Patent No.2,499,368, dated March 7, 1950, to De Groote and Keiser.' In said patentsuch test for emulsification using a water-insoluble solvent, generallyxylene, is described as an index of surface activity.

The above mentioned test, Le. a conventional emulsification test, simplymeans that the preferred product for demulsification is soluble in asolvent having hydrophobe properties or in an oxygenated water-insolublesolvent, or a mixture containing a fraction of such solvent with theproviso that when such solution in a hydrocarbon solvent is shaken withwater the product may remain in the nonaqueous solvent or, for thatmatter, it may pass into the aqueous solvent. In other words, althoughit is xylene soluble, for example, it may also be water soluble to anequal or greater degree.

For purpose of convenience, what is said hereinafter will be dividedinto four parts:

Part 1 is concerned with the oxyalkylation of glucose broadly so as toobtain products within the compositional limits of the herein describedinventional limits of the herein describedinvention; 1

Part '2 is concerned with binary or tertiary products derived fromglucose and a single oxide, or glucose and two oxides, which may belooked upon as intermediate products. More conveniently, e binarycompositions may be considered as sub-intermediates and the tertiarycompositional products as intermediates, all of which will be plain inlight of the subsequent specification. Such intermediates are reactedwithone more component, for instance, ethylene oxide, to give thefour-component product described in Part 1, preceding.

Part 3 is concerned essentially with the oxyethylation of theintermediate described in Part 2, preceding. Need- .less to say, if theintermediatewere obtained by the use of ethylene oxide, then the finalstage would involve introduction of propylene oxide or butylene oxide.

Part 4 is concerned with uses for the products herein described, eitheras such or after modification, including applications other than thoseinvolving the resolution of petroleum emulsions of the water-in-oiltype.

PART 1 The present invention is concerned with a cogeneric mixture whichis the end product of a reaction or reactions involving 4 reactants.Assuming completeness of reaction and based on a mathematical average,the final product is characterized most conveniently in terms of the 4component reactants. This phase of the invention is described elsewherein greater detail.

In representing a mixture or an end product derived from 2 components or3 components, there is no difficulty as far as using the plane surfaceof an ordinary printed sheet. For example, a' 3-component system isusually represented by a triangle -in which the apexes represent 100% ofeach component and any mixture or reaction product in terms of the 3componentsis represented by a point in the triangular area in which thecomposition is indicated by perpendiculars from such point to the sides.

Chemists and physicists ordinarily characterize a 4- cornponent systemby using a solid, i.e., a regular tetrahedron. In this particularpresentation each point or apex represents 100% or each of the 4components, each of the 6 edges represents a line or binary mixture ofthe 2 components represented by the apexes or points at the end of theline or edge. Each of the 4 triangles or faces represent a tertiarymixture of the 3 components represented by the 3 corners or apexes andobviously signify the complete absence of the 4th component indicated bythe corner or apex opposite the triangular face.

However, as soon as one moves to a point within the regular tetrahedronone has definitely characterized and specified a 4-cornponent mixture inwhich the 4 components add up to 100%. Such a representation of a '4-component system is described in detail in U.S. Patent 2,549,438 to DeGroote et al.

The invention will be described by reference to the accompanyingdrawings, which illustrate, in conventional graphical form, compositionsused in accordance with the invention in terms of the four components.In the drawings, Figure l is a conventional tetrahedron in which atrapezoidal area is blocked out and which defines the scope of theinvention. Figure 2 is a planar figure by which, having a fixed amountof one constituent, the other three may be determined.

Referring now to Figure l, the composition represented by the blockwhich is really a truncated triangular pyramid is designated by E, H; F,I; and G, I. Bear in mind that the base of the truncated pyramid, thatis E, F, G, does not rest on the bottom of the equilateral basetriangle. Point D represents 100% ethyleneoxide. The base trianglerepresents the three other components and obviously ethylene oxide. Forpurpose of what is said herein, the lower base'of the truncated pyramid,E, F, G, is a base parallel to the equilateral triangle, but two unitsup, i.e. representing 2% of ethylene oxide. Similarly, the upper base ofthe truncated pyramid H, I, J lies in a plane which is 39.5 units upfrom the base to wit represents 39.5%. ethylene oxide. Specifically thenthis invention is concerned with the use of components in whichv theethylene oxide component varies from 2% to 39.5% ethylene oxide. Theproblem then presented is the determination of 'the other threecomponents to wit butylene oxide propylene oxide and glucose.

A simplification of the problem of characterizing a 4- component system'which enters into the spirit of the present invention'is this: ,If theamount of one component is'determined or if a range is set for example2% to 39.5% of ethylene oxide then the. difference between this amountand 100% 'ji.e. 60.5% to 98% represents the amounts of percentages ofthe other three components combined and these three componentsrecalculated to bases can be determined by use of an ordinary triangulargraph.

Actually, as far as the limiting points in the truncated pyramid areconcerned, which has been previously referred to in Figure 1, it will benoted that in the subsequent text there is a complete table giving thecomposition of these points for each successive range of ethylene oxide.In other words, aperfectly satisfactory repetition is available by meansof these tables from a practical standpoint without necessarilyresorting to data of Figure'2.

v Figure 2 shows a triangle and the three components other than ethyleneoxide. These three components add- ,ed together are less than 100%, towit, 60.5% to 98%,

' but for reasons explained" are calculated back to 100%.

This 'point is clarified subsequently by' examination of the tables. 'Itwill be noted that Figure 2 shows a triangle 1, 4 and 6, which'represents the bases (top, bottom, or for that matter, intermediate) ofthe truncated pyra mid, also the areain composition which isparticularly pertinent to the present invention.

PART 2 As has been previously pointed out, the compositional limits ofthe herein described compounds are set by a truncated triangular pyramidwhich appears in Figure 1. It would be immaterial since the figure A,B,'C, D, is a regular tetrahedron whether one considered A, B, C, as thebase, B, C, D, as the base, A, C, D, as the base, or A, B, D, as thebase. In order to eliminate repetitious description which is obvious inlight of the examples included, we have selected A, B, C as the base.Another reason for so doing is that the preference is to use ethyleneoxide as the final component and this selection of A, B, C, as the baselends itself most readily to such presentation.

As has been suggested previously it is simplest to refer to Figure 2 andconcern oneself with a 3-component system derived from glucose,propylene oxide and butylene oxide. Such product can then be reactedwith 2% to 39.5% of ethylene oxide based on the final composition so asto give the preferred examples of the instant invention.

Returning now momentarily to the preparation of the 3-componentintermediate shown in Figure 2, it is obvious that hardly any directionsare required to the composition of the initial reactants based on thetriangle in the attached drawing, it will be noted that we havecalculated the percentage of the three initial reactants for points 1 to23, inclusive, so as to yield the intermediate derived from glucose,propylene oxide, and butylene oxide. These points determine not only thetriangle but also numerous points within the triangle. Furthermore,

' the points are selected so the area is divided into five parts, threeof which are triangles and two of which are four-sided figures. Thetriangles are defined by the points 1, 2 and 8; 2, 3 and 8; 5, 6 and 7;and the four-sided figures by the points 3, 4, 5 and 9 and finally 3, 8,7 and 9.

Note that these data are included in Table I (see column 9).

Note the first column gives various points on the boundary of thetriangle or within the triangle. Note the next three columns representthetertiary mixture corresponding to the initial reactants, i.e., theintermediate. These values represent percentages, by weight, of glucose,butylene oxide and propylene oxide. Thus, it is apparent that one canselect any particular point in Figure 2 and simply use the appropriateamount of oxide to obtain the selected intermediate. For instance, inregard to point 1, all that would be necessary would be to mix 86.5pounds of propylene oxide with 12.5 pounds of butylene oxide and use themixture to oxyalkylate one pound of glucose.

TABLE I Tertiary Mixture, Binary Intermediate Mixtures, Points onPercent Basis Percent Basis Boundary of Area Glucose Propylene ButyleneGlucose Propylene Glucose Butylene Oxi e Oxide Oxide Oxide 1. 86. 12. 5l. 14 98. 86 7. 42 .92. 1. 0 63. 0 36. 0 l. 56 98. 44 2. 70 97. 3 1.050.0 49.0 1.96 98.04 2.0 98.0 1. 0 24.0 75.0 4.0 96.0 1. 32 98. 68 21.021. 0 58. 0 50. 0 50. 0 26. 55 73. 45 48.5 17.0 34.5 74.5 25.5 58.4 i41.6 36. 0 36. 0 28. 0 50. 0 50. 0 56. 3 43. 7 22. 5 55. 0 22. 5 29. 071.0 50. 0 50. 0 33.0 33.0 34.0 50.0 50.0 49.2' 50.8

Similarly, in Example 2, one need only mix 63 pounds of propylene oxidewith 36 pounds of butylene and use the mixture to oxyalkylate one poundof glucose in a manner previously indicated.

Note that the fifth and sixth columns represent binary mixtures; forinstance, in regard to the various points on the triangle and within thetriangle we have calculated the initial mixture using glucose andpropylene oxide'in the first place and using glucose and ethylene. oxidein the second place, which could be employed -for-subsequentoxyalkylation to give the particular composition required. Statedanother way, we have calculated-the composition for thesub-intermediateswhich, .when .reacted with the other oxide, propyleneoxide or butylene oxide as the case may he, gives the intermediate,i.e., the three component product.

Note that a binary intermediate for the preparation of point 1 can beprepared in any suitable manner involving 1.14 pounds of glucose and98.86 pounds of propylene oxide.

Referring now to the tertiary mixture table, it. is .apparent that forpoint 1 glucose and propylene oxide together represent 87.5% andbutylenebxide 12.5%. Therefore, one could employ 87.5 pounds of thebinary :mixture (21 sub-intermediate) and react it withflZVz pounds ofbutylene oxide to give'the three-component product (the intermediate).

Similarly, in regard to the fifth and sixth columns, the mixtureinvolved glucose and propylene oxide. One could employ 1.56 pounds ofglucose and 98.44 pounds of propylene oxide. Such mixture need-only bereacted with butylene oxide in the proportion of 64 pounds of suchmixture and 36 pounds of butylene oxide to give the desired 3-componentproduct. This is obvious from the data in regard to the tertiarymixtures.

Referring now to columns 7 and 8, it is obvious one could produce anoxybutylated. glucose and then subject it to reaction with propyleneoxide. Using this procedure in regard to point 1, it is obvious themixture is obtained by 7.42 pounds of glucose and 92.58 pounds ofbutylene oxide. This product can then be subjected to reaction withpropylene oxide in the ratio of 13.5 pounds of the mixture and 86.5pounds of propylene oxide. Similarly, in regard to point 2, it isobvious that one can react 2.70 pounds of glucose with 97.3 pounds ofbutylene oxide. 37 pounds of this mixture can then be reacted with 63pounds of-propylene oxide.

As previously pointed out, the oxyalkylation of glucose has beendescribed in the literature and is described also in detail above. Allone need do is employ such conventional' oxyalkylation procedure toobtain products corresponding to the composition as defined. Attentionis again directed to the fact that one need not add the entire amount ofeither oxide at one time but that a small portion of one could be addedand then another small portion of the other, and the process repeated.

For purpose of illustration, we have prepared examples three diiterentways corresponding to the compositions of the so called intermediate inFigure 2. In the first series, butylene oxide and ethylene oxide weremixed; this series is indicated as la, 2a, 3a, through and including23a; in the second series, which represents our preferred procedure,butylene oxide was used first, followed by propylene oxide. This serieshas been indicated as 1b,

2b, 3b, through and including 23 b. Finally, in the third seriespropylene oxide was used first, followed by butylene oxide and theseries identified as 1c, 2c, 3c, through and including 23c:

TABLE II Composition Composition Composition where Butyl- Where Propyl-Composition Corresponding where Oxides ene Oxide ene Oxide to followingPoint are Mixed .used first used first Prior to Oxyfollowed byfollowedby alkylation Propylene Butylene Oxide Oxide (in 6b 6e 15a 15b15a 16a. 16b 16c 22a 22b 22c The products illustrated by the precedingexamples are not, of course, the final products of the presentinvention. They represent intermediates. However, such intermediatesrequire treatment with ethylene oxide to yield the product of thepresent invention.

11 PART 3 In Part 2 preceding there has been described the preparationof sub-intermediates and intermediates.

jected to conventional oxyethylation to produce the products describedin the present invention. The amount of ethylene oxide employed is suchthat the final composition conforms to the composition set forth inFigure 1. This means that the amount of ethylene oxide used as areactant represents 2% to 39.5% of the finalproduct with the provisothat the remainder of the product is represented by the three remainingcomponents within the proportions set forth in Figure 2.

In preparing examples we have done nothing more except use conventionaloxyethylation, using an alkaline:

catalyst such as powdered caustic soda or sodium methyl! ate. 110 C. to135 C. We have used oxyethylation pressures of 10 pounds per square inchup to 30 pounds per square inch, but usually not over 15. pounds persquare inch. The time period has varied from 15 minutes when just asmall amount of oxide was employed, up to as much as 4 to 6 hours when alarger amount of oxide was used.

Obviously the simplest of calculations is involved although we havegiven the data in tabular form for the reason that we have indicatedthat the product containing 2% of ethylene oxide carries the designationA; the one having ethylene oxide carries the designation B; the onehaving ethylene oxide is C; the one having is D; the one having is E;and the one having is 'F. Similarly, designations G, H, I, J, K, and Lare products containing 27.5% to 39.5% of ethylene oxide, respectively,as shown in Table III.

TABLE III [Proportions by Weight.]

3-Compo Ethylene nent Inter- Ex.No. Oxide mediate of Designation Part 2,

Preceding 23 77 24 76. 25 75 F. 27.5 72.6 G. 30.0 70 H. 32.5 67.5 I.35.0 65 .T. 37.5 ..62.5 K. 39.5 60.5 L.

Since it would be impossible to prepare all the variants which have beenpreviously suggested, we have proceeded as follows: We have preparedexamples corresponding to the 23 points in Figure 2 by varying theamount of ethylene oxide from 2% to 39.5 One example we have used2%,-another 5 another 10%, another 15%, another 20% and another 25%, andon up to 39.5%, as shown. The intermediates used are those described inTable II preceding. The prepared products have been described asfollows: A-la, B-2b, O3c, D-4a, etc. A-1a is, of course, the productobtained by As previously noted, these intermediates need only be sub Wehave operated at temperatures varying from using 98% of intermediate 1apreviously described in Table II, and 2%, by weight, of ethylene oxide;Example B-2b is obviously obtained by reacting by weight, ofintermediate 21; with 5% by weight, of ethylene oxide. Example C-3c isobtained by reacting 90%, by weight, of intermediate 30 with 10%, byweight, of ethylene oxide. Example D-4a is obtained by reacting 85% ofintermediate 4a with 15%, by weight, of ethylene oxide. Example E-Sb isobtained by reacting 80% of intermediate 5b with 20%, by weight, ofethylene oxide. Example F-6c is obtained by reacting 75% of intermediate60 with 25 of ethylene oxide. 7

It will be noted that the last series of 7 examples in Table IV areconcerned with compositions corresponding to points 1, 5, 10, 15, 16, 20and 23 in Figure 2. In these, instances the compound having the Fdesignation has 25% ethylene :oxide; the one with a G designation has 27/z%; the one with the H designation, 30%; the one with the Idesignation, 32 /2; the one with the I designation, 35% the one withtheK designation, 37 /2%; and the one with the L designation, 39 /2 Notethat in one instance the table shows all three types of preparation,that is in the instance of J 16a, 11612, and J 16c. The remainingexamples in Table IV, following, are self-explanatory.

TABLE IV Composition Composition Composition where 021- where ButylwherePropyl- Cornpositlon Correspondides are ene Oxide ene Oxide ing tofollowing Point Mixed Prior used first used first to Oxyalkylfollowed byfollowed by etlon Propylene Butylene Oxide Oxide A-la 1b 1c 2a 13-2!) 203a 3b C-3c D-4a 4b 4c 50 E-5b 6a 6b F-tic A-7u 7b 7a 8a 13-8!) 80 9a 9b0-90 D-10a 10b 11a E-11b 12a 12b F-l2c A-13a 13b 13c 14d 13-1417 15a15!) 0-156 D-lfia 16b 17a E-17b 18a 18b F-18c A-19a 19b 19c 2011 13-20!)200 21a 21b C-Zlc D-22a 22b 220 23a E-23b 230 1a 1b F-lc G-fia 5b 5::10a H-iOb 10c 15a 15b I-15c J-lfia .T-16b J-16c 20a K-ZOb 20a 23a 23bL-23c The same procedures have been employed using other butylene oxidesincluding mixtures having considerable isobutylene oxide and mixtures ofthe straight chain isomers with greater or lesser amount of the 2,3isomer.

Where reference has been made in previous examples to the straight chainisomer, the product used was one which was roughly 85% or more of the1,2 isomer and approximately 15% of the 2,3-cisand the 2,3-trans isomerwith substantially none or not over 1% of the isobutylene oxide.

In the preceding procedures one oxide has been added and then the other.One need not follow this procedure. The three oxides can be mixedtogether in suitable proportions and subsequently subjected to jointoxyalkylation so as to obtain products coming within the specifiedlimits. In such instances, of course, the oxyalkylation may be describedas random oxyalkylation insofar that one cannot determine the exactlocation of the butylene oxide, propylene oxide or ethylene oxidegroups. In such instances the procedure again is identically the same 13as previously described, and, as a matter of fact, we have used suchmethods in connection with glucose.

If desired, one may add part of one oxideand then all the others andthen return to the use of the first oxide. For example, one might usethe procedure previously suggested, adding some butylene oxide, all thepropylene oxide, all the ethylene oxide and then the remainder of thebutylene oxide. Or, inversely, one may add some propylene oxide, thenall the butylene oxide, then the remainder of the propylene oxide, andthen the ethylene oxide. Or, any one of the three oxides could be addedin portions so one oxide is added first, then the other two, then thefirst oxide is added again, then the other two.

we have found no advantage in so doing; indeed, our

preference has been to add all the butylene oxide first, then all thepropylene oxide, and then the required amount of ethylene oxide.

As previously pointed out, glucose can be oxyethylated in the same wayit is oxybutylated, i.e., by melting the glucose, using a suitablecatalyst, particularly an alkaline catalyst, and adding the ethyleneoxide. The changes previoulsy mentioned are of difference in degreeonly. In other words, oxyethyl-ation will take place at a lowertemperature, for instance, a top temperature of probably 110 to 135? C.instead ofl45 to 150 C. The same weight of ethylene oxide could be addedin 75% to 85% of the time required for butylene oxide. The pressureduring the reaction, instead of being 20 to 35 pounds as in the case ofbutylene oxide, is apt to be to 30 pounds and at times a little higher,but frequently operates at pounds per square inch or less. Otherwise,there is no difierence. Note, however, that it is easier and preferableto oxyethylate last, i,e., have 'a liquid reaction product obtained bythe use of butylene oxide or propylene oxide, for a combination of thetwo before the oxyethylation step. t

1 Also, if desired, the use of ethylene carbonate is a very convenientway of oxyethylating glucose. In fact, it can be oxyethylated withoutthe use of pressure.

' One can oxyalkylate using an acid catalyst or an alkaline catalyst orat least in part, without the use of any catalyst although suchprocedure is extremely slow and uneconomical. In other words, any one ofthe conventional catalysts used in oxyalkylation may be employed. It isour preference, however, to use an alkaline catalyst such as sodiummethylate, caustic soda, or the like.

Actually, glucose maycontain 1%, or somewhat less, of water. When suchglucose is heated'to 140 to 150 and subjected to vacuum, particularlywhen anhydrous nitrogen is passed through the melted mass, the resultantproduct appears to become substantially water free. Even so, there maybe a few tenths of a percent and perhaps only a trace of Water remainingin some instances.

The products obtained by the above procedure usually show some colorvarying from a light amber to a pale straw. They can be bleached in theusual fashion, using bleaching clays, charcoal, or an organic bleach,such as peroxide or peracetic acid, or the like.

Such products also have present a small amount of alkaline catalystwhich can be removed by conventional means, or they can be neutralizedby adding an equivalent amount of acid, such as hydrochloric acid. Formany purposes the slight amount of residual alkalinity is notobjectionable.

There are certain variants which can be employed without detracting fromthe metes and bounds of the invention, but for all practical purposesthere is nothing to be gained by such variants and the result is merelyincreased cost. For instance, any one of the two oxides can be replacedto a minor percentage and usually to a very small degree, by oxide whichwould introduce substantially the same group along with a side chain,for instance, one could employ glycidyl methyl ether, glycidyl ethylether, glycidyl isopropyl ether, glycidyl butyl ether or the like. p

In the hereto appended claims reference has been made to glycol ethersof glucose. Actually, it well may be that the products should bereferred to as polyol ethers of glucose in order to emphasize --the factthat the final products of reaction have more than two hydroxylradicals. However, the products may be considered as hypotheticallyderived by reaction of glucose with the glycols, such as ethyleneglycol, butylene glycol, propylene glycol, or polyglycols. For thisreason there seems to 'be a preference to usethe terminology glycolethers of glucose.

Attention again is directed to what has been said previously, to wit,that the four reactants as exemplified by the truncated triangularpyramid E, F, G, H, I, J, in the regular tetrahedron, A, B, C, D, asshown in Figure 1, might just as well be presented from any otherposition, that is, a position in which A, C, D, happen or B, C, D, or A,B, D, happen to be the base instead of A, B, C. However, such furtherelaboration would add nothing to what has been said previously and isobviously omitted for purpose of brevity.

PART 4 As to the use of conventional demulsifying agents reference ismade to US. Patent No. 2,626,929, dated January 7, 1953, to De Groote,and particularly to Part 3. Everything phat appears therein applies withequal force and effect tothe instant products, noting only that wherereference is made to Example 13b in said tex-tbeginning in column 15 andending in column 18, reference should be-to Example J-16b, hereindescribed. .ZThe compounds derived in the manner previously described,may be used as such for breakingpetroleum emulsions of the water-in-oiltype. They also can be converted into derivatives of the kindsubsequently de scribed which also may be used for this same purpose.Such derivatives are useful for other. purposes including the samepurpose for which the herein described products are effective. 1 Theherein described products. may be used for various purposes wheredetergents, common solvents, emulsifiers, and the like are used. Theymay be used as lubricants and as additives to fluids used in hydraulicbrake systems; they may be used as emulsifying agents to emulsify orremove greases or dirt; they may be used in the manufacture of a varietyof other materials such as soluble oils, insecticide sprays, etc.

These products may be combined with a variety of reactants as chemicalintermediates, for instance, with various diepoxides or polyepoxides.They may be combined with a number of other monoepoxides, such asepichlo-rohydrin, styrene oxide, glycide and methylglycide. They may bereacted with allyl glycidyl ether, glycidyl isopropyl ether, andglycidyl phenyl ether.

Furthermore, such products may be reacted with alkylene imines, such asethylene imine or propylene imine, to produce cation-active materials.Instead of an imine, one may employ what is a somewhat equivalentmaterial, to wit, a dialkylaminoepoxypropane of the structure HMLNwherein R and R" are alkyl groups.

The products may be combined with carboxy acids such as higher fattyacids, so as to change their characteristics or with polycarboxy acids,such as diglycolic, maleic acid, phthalic acid, succinic acid, and thelike, to give resins, soft polymers, or fractional esters which areessentially monomeric. Such products and others herein described, mayall be used for the resolution of petroleum emulsions of theWater-in-oil type. The products without further reaction areparticularly valuable as additives for lubricating oils which arederived from sources other than petroleum.

The addition of the oxyalkylene chain, and particularly the oxypropylenechain, to polyols produces effects at times impossible to predict andeven difficult to evaluate after being recognized. For instance, thereaction of glucose with propylene oxide to yield a hydroxylatedmaterial which can be reacted with polycarboxy acids, particularlydicarboxy acids, to give fractional esters or polymers is well known.Such products are excellent demulsifying agents. Certain polyolsparticularly having 3 or more hydroxyls, as for example glucose, whenreacted with 33 to 50 parts by Weight of propylene oxide yieldderivatives which without any further reaction of any kind are effectivedemulsifying agents. Such derivatives are also eifective for otherpurposes, such as an anti-fogging agent in motor fuels, a coagulationpreventive in burner oils, and as an additive for the prevention ofcorrosion of ferrous metals. Such invention, however, is not part ofwhat is herein claimed.

The herein described products and the derivatives thereof areparticularly valuable in flooding processes for recovery of oil fromsubterranean oil-bearing strata when employed in the manner described inU.S. Patent No. 2,233,381 dated February 25, 1941, to De Groote andKeiser.

Having thus described our invention, what we claim as new and desire toobtain .by Letters Patent is:

1. A cogeneric mixture of a homologous series of glycol ethers ofglucose; said cogeneric mixture being derived exclusively from glucose,butylene oxide, pro.- pylene oxide and ethyleneoxide in such weightproportions, so that the average composition of said cogeneric mixturestated in terms of the initial reactants, lies approximately within thetruncated triangular pyramid identified as E, H, F, I, G and J in Figure1, with the proviso that the percentage of ethylene oxide is within thelimits of 2% to 39.5%, by weight, and. the remaining three initialreactants recalculated to 100% basis, lie approximately within thetriangle defined in Figure 2 by points 1, 4 and 6.

2. The mixture of claim 1 with the proviso that oxyal-kylation takesplace in presence of an alkaline catalyst.

3. The mixture of claim 1 with the proviso that oxyalkylation takesplace in presence of an alkaline catalyst and that the butylene oxide beadded first.

4. The mixture of claim 1 with the proviso that oxyalkylation takesplace in presence of an alkaline catalyst and that the butylene oxide beadded first, and with the further proviso that the tbutylene oxide issubstantially free from isozbutylene oxide.

5. The mixture of claim 1 with the proviso that oxyalkylation takesplace in presence of .an alkaline catalyst and that the tbutylene oxidebe added first, and with the further proviso that the butylene oxideconsists of of the 1,2-isomer and approximately 15% of the 2,3-isornericform, and is substantially free trom isobutylene oxide.

6. The cogeneric mixture of claim 5 with the proviso that the reactantcomposition falls within the triangle defined by points 1, 2, and 8 inFigure 2.

7. The cogeneric mixture of claim 5 with the proviso that the reactantcomposition falls within the triangle defined by points 2, 3 and 8 inFigure 2.

8. The cogeneric mixture of claim 5 with the proviso that the reactantcomposition falls within the four-sided figure defined by points 8, 3, 9and 7.

'9. The cogeneric mixture of claim 5 with the proviso that the reactantcomposition falls within the four-sided [figure defined by points 3, 4,5 and 9.

10. The cogeneric mixture of claim 5 with the proviso that the reactantcomposition [falls within the triangle defined by points 5, 6 and 7.

References Cited in the, file of this patent UNITED STATES PATENTS2,552,528 De Groote May 15, 1951 2,574,544 De Groote Nov. 13, 19512,594,542 De Groote et al Apr. 29, 1952 2,652,394 De Groote Sept. 15,1953 2,677,700 Jackson et a1. May 9, 1954

1. A COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OFGLUCOSE, SAID COGENERIC MIXTURE BEING DERIVED EXCLUSIVELY FROM GLUCOSE,BUTYLENE OXIDE, PROPYLENE OXIDE AND ETHYLENEOXIDE IN SUCH WEIGHTPROPORTIONS SO THAT THE AVERAGE COMPOSITION OF SAID COGENERIC MIXTURESTATED IN TERMS OF THE INITIAL REACTANTS, LIES APPROXIMATELY WITHIN THETRUNCATED TRIANGULAR PYRAMID IDENTIFIED AS E, H, F, I, G AND J IN FIQURE1, WITH THE